Detergent and method of making



Re. v23,823

May 4, 1954 H. A. MoLTENl ETAL DETERGENT AND METHOD oF MAKING THE SAMEOriginal Filed March Q 1950 S S hw Ressued May 4, 1 954 UNITED STATESPATENT OFFICE DETERGENT AND METHOD OF MAKING THE SAllIE Ware @riginalNo. 2,635,103, dated April 14, 1953, Serial No. 148,692, March 9, 1950.Application for reissue June 17, 1953, Serial No. 362,430

8 Claims.

(Cl. i560-400) Matter enclosed in heavy brackets j appears in theoriginal patent but Aforms no part oi' this reissue specification;matter printed in italics indicates the additions made by reissue.

The present invention is directed to detergents and more particularly tosynthetic detergents and compositions containing the same, and methodsof making such detergents.

The present invention has among its objects the provisions of a methodof making condensation products usable for detergent purposes which issimple and highly eiective, and is adapted to large scale operation withcontrollable and reproducible results.

lt is also among the objects of the present invention to provide acondensation product which is stable, light in color, highly resistantrancidity and having excellent detergent properties.

It is further among the objects of the present invention to provide ashampoo composition in cluding said condensation product which issmooth, stable over a long period of time under adverse conditions andhighly effective in its detergent properties.

Itis still further among the objects of the present invention to providea detergent in the form of a cake, which is coherent and does notdisintegrate on handling, which is sumciently soluble te enable its usein ordinary washing operations and which may be readily produced on alarge scale.

In practicing the present invention there is provided a water-solublesalt of [hydroxyethyb sulphuric] hydrozcyethylsulphoaic acid. This ismixed with a fatty acid or a mixture of fatty acids and preferably thehigher saturated fatty acids. For example, one may use the fatty acidsobtained by hydrolysis of coconut oil or may take certain fractions ofsuch fatty acids. The fatty acids include lauric, [hydristic] myrz'stic,palmitic and stearic. Preferably saturated higher fatty acids having atleast 12 carbon atoms are used and sometimes it may be advisable toavoid the presence of any substantial amount of the unsaturated fattyacids; in such case, the fatty acids have an iodine number of not over2.0.

The relative proportions of the constituents are such that there ispresent for each mol. of the [hydroxyethylsulphuric]hydror'yethylsuiphonic acid salt an amount of the fatty acid which isless than l mol., say 0.95 mol., and more than 0.6 mol. The mixture isheated in a closed reaction kettle while maintaining an inert atmosphereby the use of a suitable gas such as nitrogen or carbon dioxide. Theheating is conducted at a temperature of about 200 to 300 C. for asuiiicient length of time to complete the reaction between theconstituents. Usually from 1 to 4 hours is suflicient. A pressure ismaintained which is usually somewhat below atmospheric but in all casesabove 250 mm. After the substantial completion of the reaction thepressure is reduced to below mm. and preferably to as low a point aspractical in ordinary production equipment, say. from 'l0 to 20 mm. Theheating is continued for a suicient length of time at the high vacuum toVolatilize and remove any unreacted fatty acid present in the reactionproduct. It is desirable that the product have a very low free fattyacid number, say, not over 5.0 and often as low as 2.0.

Usually a considerable excess of the [hydroxyethylsulphuric]hydroryethylsulphom'c acid salt is used and it may be desirable toremove such excess from the reaction product. This can be accomplishedby dissolving the reaction product in water and recrystallizing the sameby usual methods, whereby the [hydroxyethylsulphuric]hydroyethylsulphonc acid salt remains, in solution. By this procedure itis found that the iinal product is dry and granular, and isnonhydroscopic.

In the accompanying drawing constituting a part hereof and in which likereference charac ters indicate like parts, the single iigure is adiagrammatic view of an apparatus which may be used in practicing thepresent invention.

The reactor i is a closed vessel having a stirrer 2 therein mounted on avertical shaft the reactor having a well 4 therein for a thermocouple orthe like. A driving means 5 is provided :for rotating the stirrer. Thereactor is provided with an inlet E for carbon dioxide and an outlet lvapors produced in the reaction.

Vapors pass through vertical pipe a into conn denser 9, which may beWater cooled, the condensate passing out of the condenser through linei0 and into a receiver H. Gases therefrom may be vented through pipe l2and liquid from the receiver may be drained off through pipe I3. Areceiver M is provided for the purpose of catching drippings from vaporlines l and 8.

Connections l5 from the top and bottom of receiver!! lead into receiverl5 and outlet il therefrom is connected to a source of vacuum. Liquidfrom receiver Hi may be removed through pipe I3. A bypass i9 is providedtrom receiver i I to the source of vacuum.

The following are examples of the operation of the invention.

Example 'l 1 mol. of [hydroxyethylsulphuricl ieg/droeg ethylsulphom'cacid sodium salt and 0.8 mol. or

a mixture of fatty acids in which lauric acid is the major constituent,containing not over 30% of the adjacent fatty acids and derived from thefractional distillation of the fatty acids of coconut oil, are heated inan atmosphere of carbon dioxide to 220 C.-260 C. and maintained at saidtemperature for 2 hours or more. The pressure is maintained at about 300mm. absolute pressure or somewhat higher for the aforesaid period untilthe reaction is substantially complete. The pressure is then decreasedas rapidly as possiblei to not over 20 mm. and maintained at saidtemperature so that the total elapsed time is at least 4 hours, of whichabout 1.5 hours is at the lowest pressure.

The mass is cooled as rapidly as possible with continuous agitation. Asthe cooling proceeds the physical condition of the reaction mass changesfrom a non-viscous liquid to a viscous mass and then to a brittle masswhich granulates readily and forms powder or beads. After the contentsof the reaction vessel have reached a relatively 10W temperature, saybelow 120 C., the mass may be removed. To further pulverize the mass toa uniform size, it is cooled to room temperature. The free fatty acidnumber of the product is approximately 5.0. During the entire operationoxygen is excluded from the reaction vessel.

To purify the product by removing unreacted Example 2 A mixture is madeof 1 mol. equal to 14S lbs. of sodium hydroxy [ethysulphate]ethylsulphonate and .8 mol., equal to 175 lbs. of commercial lauricacid. Said acid is derived by the hydrolysis of hydrogenated coconut oiland fractional distillation thereof to give a lauric acid fraction,which contains a major portion of lauric acid and a minor portion ofadjacent acids. typical mixture has a free fatty acid number of 126l to132, a maximum iodine value of 2.0, a titre of about 24 C. as a minimum,and a saponification value of 250 to 263.

The mixture is heated in the reactor to a temperature of 220 to 260 C.in an atmosphere of CO2 and at approximately 400 mm. absolute pressure.The heating at this temperature is continued for 2 hours or more, afterwhich the pressure is decreased rapidly to less than 20 mm. absolutepressure, While maintaining approximately the same range oftemperatures. Temperature and low pressure are maintained for at leastan hour and a half and sufliciently long so that the total time ofheating is at least 4 n 4 [ethylsulphate] ethylsulphonate equal to 111lbs., with .8 mol. of commercial stearic acid, equal to 162 lbs. Atypical stearic acid composition has a free fatty acid number of 99 to105, a maximum iodine value of 3.0, a saponiiication value of 197 to205, and a titre of 61 to 64 C. The procedure of Example 2 is followed.

Example 4 A mixture is made of 'l mol. of sodium hydroxy [ethylsulphate]eth1/lsulphonctte` and .8 mol. of commercial lauric acid. The acid isderived from coconut oil, as described in Example 2, the lower boilingfraction being separated from the lauric acid fraction. A typicalcomposition has a free fatty acid number of 126 to 132, a saponificationvalue of 251 to 263, an iodine value of 8 to 16 and a titre of 24 to 28C. The procedure of Example 2 is followed.

Example 5 Any of the above compositions may be made into a creamshampoo. In making such a shampoo a stabilizing material is used and itis dispersed in water. Then a relatively large amount of the aforesaidproduct, which is the detergent, is added, together with salt andlanolin. The mixture is agitated with a suitable type of agitator and issimultaneously heated preferably on a steam bath to 50-75 C. Agitationis continued until the composition is smooth and creamy. The compositionwhile still at elevated temperature is homogenized in a suitable mixerfor about l0 minutes, poured into containers and allowed to cool. Thefollowing is a typical composition in parts by Weight:

Polyvinyl alcohol 2 Water 'il Product of Example 2 23 Product of Example3 2 Stearic acid (comm.) 1 Sodium chloride i Lanolin l Example 6 Thefollowing composition is quite suitable as a shampoo, the parts being byweight:

Methylcellulose 0.5 Arylalkylsulphonate (Na) 0.5 Water '71.0 Product ofExample 2 23.0 Product of Example 3 2.0 Stearic acid 1.0 Sodium chloride2.0 Sodium hydroxide 0.14 Lanolin 1.0'

Example "I In order to produce the detergent in a bar or cake form anyone of the reaction products oi Examples l to 4 is heated to a pointsubstantially above room temperature, say 50 to 100 C. 5 to 'l0 parts byWeight of water at about the boiling point is mixed thoroughlytherewith. When the composition is uniform it is cast in molds to formcakes of suitable size and In a typical composition 9 parts of thecondensation product may be mixed with l part of water to form asatisfactory cake. If desired, addition agents, fillers, abrasives,coloring materials, perfumes or the like may be introduced during themixing operation.

The procedure is based upon the discovery that the condensation productshave steep solubility curves so that when heavy suspensions thereof incold water are warmed, they go through a pasty stage before giving clearsolutions. In view of this an insufficient amount of water to give aclear solution when hot is introduced into the condensation product andupon cooling it rapidly goes through the pasty and then into the solidstate to form a dry coherent body even though a substantial amount ofwater is present therein.

Although the invention has been described setting forth several specificembodiments thereof, the invention is not to be limited thereto asvarious changes in the details of operation and of composition may bemade without departing from the principles herein set forth. Forinstance, instead of using the sodium salt of the[hydroxyethylsulphuric] hydroxyethysulphonic acid, other soluble saltsmay be used, as for example, the potassium salt. Such substitution maybe made in any of Examples 1 to 4. The acids used in the reaction maycome from other sources than coconut oil and such sources may bevegetable, animal or synthetic. Other higher fatty acids than thosespecifically named may be substituted in part or in whole for the lauricand stearic fractions set forth in the specific examples. Theproportions of the constituents may be varied to some degree and theexcess thereof may be removed in a suitable manner or may be allowed toremain in the final product in such cases where the presence of theexcess is not detrimental. The time, temperature and pressure ofoperation may be varied in co-relation so as to give the same results asset forth in Examples l and 2.

These and other changes in the details of the invention may be madeWithin the scope thereof and the invention is, therefore, to be broadlyconstrued and not to be limited except by the character of the claimsappended hereto.

We claim:

1. A method of making detergents which ccmprises mixing 1 mol. of awater-soluble [hydroxyethylsulphuric] hydromyethylsulphonic acid saltwith an amount of a higher fatty acid less than 1 and more than 0.6mol., maintaining an inert atmosphere, heating said mixture to atemperature of 200-300 C. for a sufficient length of time to cause asubstantial reaction to occur between said substances, the pressurebeing below atmospheric but above 250 mm., thereafter decreasing thepressure to below 100 mm., continuing the heating to remove free fattyacid.

2. A method of making detergents which comprises mixing 1 mol. of aWater-soluble [hydroxyethylsulphuric] hydroyethylsulphonc acid salt withan amount of a higher fatty acid less than 1 and more than 0.6 mol.,maintaining an inert atmosphere, heating said mixture to a temperatureof 230-300 C. at a pressure below atmospheric but above 250 mm. for asuicient length of time to cause a substantial reaction to occur betweensaid substances, thereafter decreasing the pressure to below 100 mm.,continuing the heating to remove free fatty acid.

3. A method of making detergents which com- S5 prises mixing 1 mol. of awater-soluble [hydroxyethylsulphuric] hydroyethylsulphom'c acid saltwith an amount of a fatty acid taken from the class consisting oflauric, myristic, palmitic and stearic less than 1 and more than 0.6mol., maintaining an inert atmosphere, heating said mixture to atemperature of 230-300 C. for a sufficient length of time to cause asubstantial reaction to occur between said substances, the pressurebeing below atmospheric but above 250 mm., thereafter decreasing thepressure to below mm., continuing the heating to remove free fatty acid.

4. A method of making detergents which comprises mising 1 mol. of awater-soluble [hydroxyethylsulphuric] hydroyeth'ylsulphonic acid saltwith an amount of a higher fatty acid less than 1 and more than 0.6mol., maintaining an inert atmosphere, heating said mixture to atemperature of 230-300 C. for a sufcient length of time to cause asubstantial reaction to occur between said substances, the pressurebeing below atmospheric but above 250 mm., thereafter decreasing thepressure to below 100 mm., continuing the heating to remove free fattyacid, and recrystallizing the product so formed to remove excess of said[hydroxyethylsulphuric] hydroxyethylsulphonic acid salt.

5. The reaction product of 1 mol. of a watersoluble[hydroxyethylsulphuric] hydrozryethylsulphom'c acid salt with about 0.6to 0.95 mol. of a higher fatty acid, produced by heating said reactantsat 200-300 C. at pressures below atmospheric and above 250 mm. in aninert atmosphere, and thereafter continuing said heating at pressuresbelow 100 mm.

6. The reaction product of 1 mol. of a watersoluble[hydroxyethylsulphuric] hydroyethylsulphom'c acid salt with about 0.6 to0.95 mol. of a higher saturated fatty acid, produced by heating saidreactants at 200-300 C. at pressures below atmospheric and above 250 mm.in an inert atmosphere, and thereafter continuing said heating atpressures below 100 mm.

'7. The reaction product of 1 mol. of a watersoluble[hydroxyethylsulphuric] hydroyethylsulphomc acid salt of an alkali metalwith about 0.6 to 0.95 mol. of a fatty acid, produced by heating saidreactants at 200-300 C. at pressures below atmospheric and above 250 mm.in an inert atmosphere, and thereafter continuing said heating atpressures below 100 mm.

8. The reaction product of 1 mol. of a watersoluble[hydroxyethylsulphuric] hydroyethylsulphonic acid salt with about 0.6 to0.95 mol. of a higher fatty acid in the form of its alkali metal salt,produced by heating said reactants at 200-300 C. at pressures belowatmospheric and above 250 mm. in an inert atmosphere, and thereaftercontinuing said heating at pressures below 100 mm.

References Cited in the le 0f this patent or the original patent UNITEDSTATES PATENTS Number Name Date 2,175,285 Duncan Oct. 10, 1939 2,204,433Muncie et al. June 11. 194'0

